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TiO2-mediated photooxidation of 1,2-ethanediol in the presence of oxygen by light of λex > 300 nm results in its C-C bond cleavage to yield HCHO. The kinetics of reaction, monitored by following the product, obeys Langmuir-Hinshelwood's equation. The reaction rate constant and the adsorption equilibrium constant for this process are evaluated to be 1.9 x 10-6 mol dm-3 s-1 and 16 dm3 mol-1, respectively. The presence of O2 and Ag+ enhance the reaction rate and the yield of HCHO by trapping the conduction band electron. The oxidation is suggested to take place by direct hole as well as by trapped hole transfer. At pH 12 the reaction efficiency has been observed to be about 14 times higher to that of at pH 2.5. About 3.4 wt% Ag+ exhibits the maximum cocatalytic effect. The participation of Ag2+ in the catalytic action is ruled out. A scheme of photocatalytic oxidation is discussed.